CN114249902B - Preparation method and application of phenoxazine-based metal organic framework with visible light catalytic reduction C-F bond performance - Google Patents
Preparation method and application of phenoxazine-based metal organic framework with visible light catalytic reduction C-F bond performance Download PDFInfo
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- CN114249902B CN114249902B CN202111609429.7A CN202111609429A CN114249902B CN 114249902 B CN114249902 B CN 114249902B CN 202111609429 A CN202111609429 A CN 202111609429A CN 114249902 B CN114249902 B CN 114249902B
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 28
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 8
- 102100022563 Tubulin polymerization-promoting protein Human genes 0.000 claims abstract description 25
- 101710158555 Tubulin polymerization-promoting protein Proteins 0.000 claims abstract description 25
- 239000013110 organic ligand Substances 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 238000006722 reduction reaction Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 238000004729 solvothermal method Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 239000013077 target material Substances 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000010898 silica gel chromatography Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 238000006392 deoxygenation reaction Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 claims description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 2
- PWYPGEFOZYBWDP-UHFFFAOYSA-N boric acid;pyridine Chemical compound OB(O)O.C1=CC=NC=C1 PWYPGEFOZYBWDP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 5
- 230000005284 excitation Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- XTGOWLIKIQLYRG-UHFFFAOYSA-N 2,3,4,5,6-pentafluoropyridine Chemical compound FC1=NC(F)=C(F)C(F)=C1F XTGOWLIKIQLYRG-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000027756 respiratory electron transport chain Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 230000005281 excited state Effects 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229930182555 Penicillin Natural products 0.000 description 3
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- UXJRQNXHCZKHRJ-UHFFFAOYSA-N methyl 2,3,4,5,6-pentafluorobenzoate Chemical compound COC(=O)C1=C(F)C(F)=C(F)C(F)=C1F UXJRQNXHCZKHRJ-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229940049954 penicillin Drugs 0.000 description 3
- 150000002991 phenoxazines Chemical class 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KHHIALZHPCMMMT-UHFFFAOYSA-N 10-(4-bromophenyl)phenoxazine Chemical compound C1=CC(Br)=CC=C1N1C2=CC=CC=C2OC2=CC=CC=C21 KHHIALZHPCMMMT-UHFFFAOYSA-N 0.000 description 2
- WPSJSDFNLWGYHA-UHFFFAOYSA-N 3,7-dibromo-10-(4-bromophenyl)phenoxazine Chemical compound C1=CC(Br)=CC=C1N1C2=CC=C(Br)C=C2OC2=CC(Br)=CC=C21 WPSJSDFNLWGYHA-UHFFFAOYSA-N 0.000 description 2
- 241001120493 Arene Species 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001501 aryl fluorides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005932 reductive alkylation reaction Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000034184 interaction with host Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMLDUMMLRZFROX-UHFFFAOYSA-N pyridin-2-ylboronic acid Chemical compound OB(O)C1=CC=CC=N1 UMLDUMMLRZFROX-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- C07C2601/14—The ring being saturated
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Abstract
The invention belongs to the technical field of photocatalytic materials, and relates to a preparation method and application of a phenoxazine-based metal organic framework with visible light catalytic reduction C-F bond performance, wherein the preparation method takes 3, 7-bipyridine-10- (4-pyridylphenyl) phenoxazine TPPP as a main organic ligand, 4' -biphenyldicarboxylic acid BPDC as an auxiliary ligand, and Zn in metal zinc salt 2+ As a node, a phenoxazine-based metal organic framework Zn-TPPP-BPDC is prepared by a solvothermal method, and the synthetic route is as follows: TPPP + BPDC + Zn 2+ → Zn-TPPP-BPDC; the preparation method is simple, the raw materials are low in price, the obtained phenoxazine-based metal organic framework material can generate weak interaction with a polyfluorinated aromatic hydrocarbon substrate under a mild condition, and photoinduced charges are separated under the excitation of visible light so as to realize C-F bond activation in a heterogeneous system and photocatalytic reduction of C-F bonds, and the method has high yield, good regioselectivity and substrate applicability.
Description
Technical Field
The invention relates to a preparation method and application of a phenoxazine-based metal organic framework with a visible light catalytic reduction C-F bond performance, and belongs to the technical field of photocatalytic materials.
Background
Partially fluorinated aromatics constitute an extremely important class of molecules in the pharmaceutical and crop science industries. In 2013, the U.S. food and drug administration approved 27 new small drug molecules, 9 of which contained C-F bonds and 4 of which contained aryl C-F bonds. Aryl fluorides also play an important role in crop protection, producing tens of thousands of tons per year of insecticides containing aromatic fluorides. Despite the simple structure of partial aryl fluorides, their synthesis often relies on either tedious traditional fluorination strategies or C-H fluorination strategies and cross-coupling strategies that require complex initial substrate syntheses, resulting in difficult practical applications. Another current way to obtain polyfluoroarenes is to use highly fluorinated or perfluorinated arenes, which are cheap and easily available, as substrates, remove the unwanted fluorine atoms, and couple other functional groups to obtain the target polyfluoroarenes. However, this strategy is also somewhat challenging because the C-F bond is thermodynamically and kinetically stable due to its short length, high bond energy, and no significant polarization. In addition, even if the C — F bond is broken, a strong metal-fluorine bond is generally formed, resulting in slow turnover of the metal catalyst and difficulty in performing the catalytic process. In addition, regioselectivity of C-F bond functionalization is also a challenge due to the multiple C-F bonds of highly fluorinated substrate arenes.
Visible light is used as green energy to excite photosensitizer to generate photoinduced electron transfer, so that reduction removal of C-F bond under mild condition can be realized, and corresponding target product is generated through further alkylation. But currently relies primarily on the photocatalytic reduction of noble metal photocatalysts and a small fraction of organic photosensitizers in a homogeneous system. In view of the high cost of noble metal catalysts and the fact that self-quenching occurs due to uncontrolled thermal motion and intermolecular collisions in homogeneous systems, a cheaper alternative photocatalytic material is needed to address these problems.
The metal organic framework is used as a heterogeneous material with reasonably designed structure and composition, can design and modify a photosensitizer, introduces a photocatalytic center, has porous characteristic, is favorable for contacting reactants and the catalytic center, can have weak interaction with host and guest molecules among substrate molecules, and is more favorable for the generation of an electron transfer process. The photosensitive centers are orderly and controllably arranged and separated through the coordination of the organic ligand and the transition metal, so that an invalid electron transfer process caused by collision can be avoided, the excited photosensitizer is easier to carry out electron transfer with substrate molecules, and a free radical intermediate is more effectively generated. The reasonable connection mode can also promote the photocatalysis circulation and the effective electron transfer process, thereby improving the catalysis efficiency.
The phenoxazine and the derivative thereof are used as a kind of modifiable photosensitive molecules, most of the phenoxazine derivatives have stronger photoresponse in a visible light region, have higher excited state reduction potential, can be applied to reduction of carbon-halogen bonds, and are currently applied to reduction of organic molecules through the excited state photoreduction capability of the phenoxazine derivatives to generate various carbon free radical intermediates, such as carbonyl free radicals, aryl free radicals, trifluoromethyl free radicals and the like.
The phenoxazine derivative is used as an organic photosensitive ligand TPPP, has good excited state photoreduction capability (-1.84V vs. SCE), and is used as a photosensitive center to synthesize the metal organic framework material photocatalyst. The ligand TPPP and the auxiliary ligand BPDC are connected by four-coordinated metal zinc nodes, so that the separation of photosensitive centers is effectively realized, and the process of self-quenching of the light-excited intermediate is inhibited to a certain extent. Meanwhile, the generated pore channels can enable substrate molecules to effectively enter, weak interaction is generated between the pore channels and a photosensitive central organic ligand TPPP, electrons are more favorably transferred to the substrate under the excitation of 385nm visible light, and the C-F bond is further broken by a reduction process. The reaction system is suitable for C-F bond reduction alkylation reaction of various polyfluorinated aromatic hydrocarbons, and the phenoxazine-based metal organic framework material is used as a novel photocatalyst to effectively solve the problems, so that a new idea is provided for fine chemical medicine synthesis.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method and application of a phenoxazine-based metal organic framework with the performance of visible light catalytic reduction of a C-F bond. The phenoxazine-based metal organic framework target material obtained by the preparation method can have weak interaction with a substrate in a pore channel, and an electron transfer process between the metal organic framework material and the substrate under a light excitation condition is promoted. Meanwhile, the composite material has a wider visible light absorption range and good thermal stability; can be recycled for many times, is beneficial to recovery, and has the advantages of simple preparation, cheap raw materials and the like.
In order to achieve the above purpose and solve the problems existing in the prior art, the invention adopts the technical scheme that: a preparation method of a phenoxazine-based metal organic framework with a visible light catalytic reduction C-F bond performance comprises the steps of taking 3, 7-bipyridine-10- (4-pyridylphenyl) phenoxazine TPPP as a main organic ligand, taking 4, 4' -biphenyldicarboxylic acid BPDC as an auxiliary ligand and Zn in metal zinc salt 2+ As a node, a phenoxazine-based metal organic framework Zn-TPPP-BPDC is prepared by a solvothermal method, and the synthetic route is as follows:
TPPP+BPDC+Zn 2+ →Zn-TPPP-BPDC；
the metal zinc salt is selected from one of zinc nitrate, zinc chloride or zinc sulfate;
the main organic ligand TPPP has the following molecular structural formula (A),
the auxiliary ligand BPDC has the following molecular structural formula (B),
the preparation method of the Zn-TPPP-BPDC comprises the following steps:
and 3, mixing the white solid powder prepared in the step 2, pyridine boric acid, tetrakis (triphenylphosphine) palladium and anhydrous potassium carbonate according to the weight ratio of 1: 3-4: 0.05-0.15: adding the mixture into a three-necked bottle at a molar ratio of 4-6, vacuumizing and introducing nitrogen for 1-3 times, then sequentially adding 100-150 mL of toluene subjected to pre-deoxygenation, 80-90 mL of ethanol subjected to pre-deoxygenation and 40-50 mL of water subjected to pre-deoxygenation, reacting for 40-50 h at 70-80 ℃, cooling the reaction solution to room temperature, transferring the reaction solution into a separating funnel, and mixing the reaction solution with the solvent in a volume ratio of 1: extracting 3-5 times with dichloromethane and water, separating liquid, drying a lower organic phase with anhydrous sodium sulfate, filtering, spin-drying filtrate to obtain a crude product, and separating by silica gel column chromatography to obtain yellow solid powder, namely the main organic ligand TPPP;
step 4, mixing the main organic ligand TPPP, the auxiliary ligand BPDC and the metal zinc salt prepared in the step 3 according to the weight ratio of 1: 2-2.5: adding 3-4 mol ratio of the mixture into a mixture with the volume ratio of 1: 1-2, adding the mixed solution of N, N-diethylformamide and ethanol into a hydrothermal reaction kettle with a polytetrafluoroethylene lining after ultrasonic dissolution assistance, sealing, placing the hydrothermal reaction kettle in an oven at 85-90 ℃ for reaction for 40-50 h, cooling to room temperature, removing a supernatant, adding ethanol for washing, and centrifuging to obtain an orange blocky crystal, namely the target material, namely the phenoxazine-based metal organic framework Zn-TPPP-BPDC.
The application of the phenoxazine-based metal organic framework prepared by the method in the photocatalytic reduction reaction of C-F bonds.
The invention has the beneficial effects that: a preparation method and application of a phenoxazine-based metal organic framework with a visible light catalytic reduction C-F bond performance are provided, wherein the preparation method is to use 3, 7-bipyridine-10- (4-pyridylphenyl) phenoxazine TPPP as a main organic ligand, 4' -biphenyldicarboxylic acid BPDC as an auxiliary ligand and Zn in a metal zinc salt 2+ As a node, a phenoxazine-based metal organic framework Zn-TPPP-BPDC is prepared by a solvothermal method, and the synthetic route is as follows: TPPP + BPDC + Zn 2+ → Zn-TPPP-BPDC; the phenoxazine-based metal organic framework Zn-TPPP-BPDC prepared by the method can obtain a product of C-F bond reduction alkylation under the irradiation of an LED with the wavelength of 385 nm. Zn-TPPP-BPDC can generate weak interaction with substrate molecules to activate C-F bonds, electrons can be better transferred to the substrate molecules under the condition of photoexcitation, and reduction alkylation on inert C-F bonds in a heterogeneous photocatalytic system under a mild condition is realized by utilizing stronger excited state reduction potential of a photosensitive central organic ligand TPPP of the Zn-TPPP-BPDC, so that the Zn-TPPP-BPDC has higher yield, good regioselectivity and substrate applicability.
Drawings
FIG. 1 is a schematic diagram of the crystal structure of the target material Zn-TPPP-BPDC of example 1.
FIG. 2 is a photo current test spectrum of the target material Zn-TPPP-BPDC and the ligand TPPP in example 4.
FIG. 3 is a graph showing the UV-VIS absorption spectrum of the target material Zn-TPPP-BPDC of example 5.
FIG. 4 is a spectrum of emission light of the target material Zn-TPPP-BPDC of example 6 after adding different concentrations of pentafluoropyridine, with an excitation wavelength of 385 nm.
FIG. 5 is an infrared absorption spectrum of Zn-TPPP-BPDC as a target material in example 6 and a target material Zn-TPPP-BPDC after immersion in an acetonitrile solution of pentafluoropyridine.
FIG. 6 is a partially enlarged plot of the infrared absorption spectra of the target material Zn-TPPP-BPDC of example 6 and the target material Zn-TPPP-BPDC after immersion in acetonitrile solution of pentafluoropyridine.
FIG. 7 is a schematic diagram of an inclusion single crystal structure of the target material Zn-TPPP-BPDC of example 7, which is obtained by soaking the target material Zn-TPPP-BPDC in a mixed solvent solution of N, N-diethylformamide and ethanol of methyl pentafluorobenzoate.
FIG. 8 is a graph showing the catalytic cycle yield of the target material Zn-TPPP-BPDC of example 8.
FIG. 9 is a PXRD pattern (calculated, experimentally synthesized and measured after three photocatalytic rounds of recovery) of the Zn-TPPP-BPDC target material of example 8.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The preparation method of the Zn-TPPP-BPDC comprises the following steps:
Step 3, weighing white solid powder 3, 7-dibromo-10- (4-bromophenyl) phenoxazine (5.00g, 10.08mmol), pyridine boronic acid (4.34g, 35.28mmol), tetrakis (triphenylphosphine) palladium (589.3mg, 0.51mmol) prepared in step 2, and anhydrous potassium carbonate (6.97g, 50.40mmol) into a three-neck bottle in sequence, vacuumizing and introducing nitrogen for 3 times, then adding 130mL of toluene deoxygenated in advance, 84mL of ethanol deoxygenated in advance, and 42mL of water deoxygenated in advance in sequence, reacting for 48h at 75 ℃, cooling the reaction solution to room temperature, transferring the reaction solution into a separating funnel, and reacting by using a volume ratio of 1: 3, extracting with dichloromethane and water for 3 times, separating liquid, drying a lower organic phase with anhydrous sodium sulfate, filtering, spin-drying filtrate to obtain a crude product, and then separating by adopting a silica gel column chromatography, wherein a developing solvent is a mixture of a solvent with a volume ratio of 1: 20: 1000 parts of triethylamine, dichloromethane and n-hexane, a yellow solid powder was obtained, i.e. 4.82 g of the main organic ligand TPPP, with a yield of 87.4%.
Step 4, weighing the main organic ligand TPPP (4.9mg, 0.01mmol) prepared in the step 3, the auxiliary ligand BPDC (4.8mg, 0.02mmol) and the zinc nitrate (7.6mg, 0.04mmol) and adding the mixture into a container with a volume ratio of 1: 1, weighing 20 bottles of penicillin bottles of a mixed solvent of N, N-diethylformamide and ethanol one by one, adding the penicillin bottles into a hydrothermal reaction kettle with a polytetrafluoroethylene lining after ultrasonic dissolution assistance, sealing, placing the hydrothermal reaction kettle in a 90 ℃ oven for reaction for 48 hours, cooling the hydrothermal reaction kettle to room temperature, removing supernatant, adding ethanol for washing, and centrifuging to obtain 89.6mg of orange blocky crystals, wherein the yield is 83%. The orange blocky crystal is the target material, namely the phenoxazine-based metal organic framework Zn-TPPP-BPDC. The crystal is tested on a SMART APEX CCD diffractometer of Bruker company, and the analysis of the single crystal structure shows that the complex Zn-TPPP-BPDC crystal belongs to a monoclinic system, P2 1 The space group/c, a is 8.1979(15), b is 23.069(5), c is 40.059(8), α is γ is 90, and β is 91.624 (5). The crystal structure of Zn-TPPP-BPDC is shown in figure 1.
Example 2
Weighing the main organic ligand TPPP (4.9mg, 0.01mmol), the auxiliary ligand BPDC (4.8mg, 0.02mmol) and zinc chloride ((5.5mg, 0.04mmol) prepared in the step 3 of the example 1, adding the main organic ligand TPPP, the auxiliary ligand BPDC and the zinc chloride into a penicillin bottle containing a mixed solvent of N, N-diethylformamide and ethanol with the volume ratio of 1: 1, weighing 20 bottles by bottle, adding the bottles into a hydrothermal reaction kettle with a polytetrafluoroethylene lining after ultrasonic dissolution assistance, sealing, placing the hydrothermal reaction kettle in an oven at 90 ℃ for reaction for 48 hours, cooling the hydrothermal reaction kettle to room temperature, removing a supernatant, adding ethanol for washing, and centrifuging to obtain orange blocky crystals with the total weight of 87.5mg and the yield of 81 percent, wherein the orange blocky crystals are the target material phenoxazine-based metal organic framework Zn-TPPP-BPDC.
Example 3
The main organic ligand TPPP (4.9mg, 0.01mmol) prepared in step 3 of example 1, the ancillary ligand BPDC (4.8mg, 0.02mmol) and zinc sulphate (6.5mg, 0.04mmol) were weighed out and added to a vessel containing a volume ratio of 1: 1, weighing 20 vials by vial, adding the vials into a hydrothermal reaction kettle with a polytetrafluoroethylene lining after ultrasonic assisted dissolution, sealing, placing the hydrothermal reaction kettle in a 90 ℃ oven for reaction for 48 hours, cooling to room temperature, removing supernatant, adding ethanol for washing, and centrifuging to obtain 79.9mg of orange blocky crystals, wherein the yield is 74%. The orange blocky crystal is the target material, namely the phenoxazine-based metal organic framework Zn-TPPP-BPDC.
Example 4
2mg of Zn-TPPP-BPDC was weighed and added to 0.5mL of ethanol to prepare a suspension, then 0.06mL of Nafion was added separately and mixed by sonication, and 0.2mL of the suspension was applied to the surface of FTO glass with an area of 1cm 2 And drying, and then clamping the FTO glass on an electrode clamp to serve as a working electrode. The photocurrent test was carried out at CHI 660E electrochemical workstation, with a three-electrode system, an Ag/AgCl electrode as a reference electrode, a platinum sheet as a counter electrode, and 0.1M acetonitrile solution of tetrabutylammonium hexafluorophosphate as an electrolyte, under a nitrogen atmosphere of 1atm, the photocurrent test was carried out at room temperature with a 50W LED light source with a wavelength of 385 nm. And photocurrent test comparison spectra of Zn-TPPP-BPDC and ligand TPPP are shown in figure 2.
Example 5
The newly synthesized material Zn-TPPP-BPDC was pipetted from the mother liquor onto filter paper, and after drying it was ground into powder with an agate mortar. Weighing about 10mg of Zn-TPPP-BPDC powder, placing the powder at the center of a groove of a quartz glass sheet, covering the groove with another quartz glass sheet, and finely adjusting the positions of the two quartz glass sheets to ensure that the powder is uniformly distributed in the groove as much as possible without gaps. The UV-VIS absorption spectrum of Zn-TPPP-BPDC is shown in FIG. 3, which reflects the light absorption property of Zn-TPPP-BPDC. The strong absorption band of Zn-TPPP-BPDC is centered at 380nm, extending from 300nm to 500 nm.
Example 6
2mg of Zn-TPPP-BPDC was weighed and added to 10mL of acetonitrile to prepare a suspension, and the suspension was titrated with pentafluoropyridine, and it was found that the fluorescence intensity of Zn-TPPP-BPDC was gradually decreased at 598nm, a new fluorescence peak was observed at 433nm, and the fluorescence peak intensity was gradually increased with the addition of the substrate, as shown in FIG. 4. Putting Zn-TPPP-BPDC into acetonitrile solution of pentafluridine with certain concentration to be soaked for three hours to obtain new crystalline solid, tabletting by using potassium bromide, testing the infrared spectrum of the solid state, wherein the test result is shown in figure 5, and the infrared spectrum of the soaked pentafluridine is shown in 1072cm -1 And 972cm -1 The peak is a stretching vibration peak of the C-F bond of the adsorbed pentafluoropyridine. And the peak of C-F bond of the separate pentafluoropyridine is 1076cm -1 And 976cm -1 As shown in fig. 6. The red shift shows that the pentafluoropyridine activates a substrate in the Zn-TPPP-BPDC pore channel through the host-guest action between the Zn-TPPP-BPDC and the fluorine-containing aromatic compound to form an electron donor-acceptor compound.
Example 7
The Zn-TPPP-BPDC prepared in the example 1 is soaked and washed for 3-5 times by N, N-diethylformamide and ethanol solution in the same volume ratio, the supernatant is colorless and clear, 0.5-1 mol/L of methyl pentafluorobenzoate is added into the supernatant, a new crystalline solid is obtained after soaking for three hours, and the crystal structure of the inclusion substrate is tested on a SMART APEX CCD diffractometer of Bruker company. The analysis of the single crystal structure shows that in the formed methyl pentafluorobenzoate @ Zn-TPPP-BPDC material, substrate molecules have pi-pi interaction with Zn-TPPP-BPDC in the pore channels of the Zn-TPPP-BPDC, and C-F bonds adjacent to benzene ring ester groups in the methyl pentafluorobenzoate of the substrate molecules are obviously elongated, as shown in FIG. 7.
Example 8
To the dried photoreaction tube, Zn-TPPP-BPDC (0.01mmol, 5 mol%) was added, and sealed with a bung. The reaction system was subjected to vacuum-pumping nitrogen-introducing cyclic operation three times to remove oxygen in the system, and dried and degassed acetonitrile (1mL), cyclohexene (1.2mmol, 6.0eq), triethylamine (1.0mmol, 5.0eq), and pentafluoropyridine (0.2mmol, 1.0eq.) were added to the reaction tube with a long needle and sealed with a sealing film. Connecting the reaction tube with condensed water and irradiating under a 385nm LED light source. After reacting for 24h at room temperature, the catalyst is separated by centrifugation, collected and put into the next catalytic cycle again, and the cycle is carried out for three times, and the catalytic cycle yield is shown in fig. 8. Compared with a PXRD spectrogram of a metal organic framework collected after three catalytic cycles and a freshly prepared PXRD spectrogram, a main characteristic peak is still well maintained, which shows that a framework structure is maintained in a reaction process, namely, a catalyst can be well recycled, and a PXRD spectrogram is shown in figure 9.
Example 9
To the dried photoreaction tube, Zn-TPPP-BPDC (0.01mmol, 5 mol%) was added, and sealed with a bung. Vacuumizing the reaction system, introducing nitrogen for three times for cyclic operation, removing oxygen in the system, adding dried and degassed acetonitrile (1mL), cyclohexene (1.2mmol, 6.0eq), triethylamine (1.0mmol, 5.0eq), polyfluorinated aromatic hydrocarbon substrate (0.2mmol, 1.0eq.) and sealing by using a sealing film into the reaction tube by using a long needle. After reacting for 24h at room temperature, the catalyst was separated by organic filtration, the filtrate was spin-dried, and the crude product was separated by column chromatography. Zn-TPPP-BPDC catalyzes the substrate expansion of C-F bond reductive alkylation as shown in Table 1.
TABLE 1
The phenoxazine-based metal organic framework Zn-TPPP-BPDC shows good para-position selectivity and functional group selectivity to the C-F bond reductive alkylation reaction of polyfluorinated aromatic hydrocarbon, and can also have a certain yield to a substrate containing a strong electron-withdrawing group for substitution, and the heterogeneous catalysis system has good application potential in the field of fine chemical pharmacy.
Claims (2)
1. A preparation method of a phenoxazine-based metal organic framework with a visible light catalytic reduction C-F bond performance comprises the steps of taking 3, 7-bipyridine-10- (4-pyridylphenyl) phenoxazine TPPP as a main organic ligand, taking 4, 4' -biphenyldicarboxylic acid BPDC as an auxiliary ligand and Zn in metal zinc salt 2+ As a node, a phenoxazine-based metal organic framework Zn-TPPP-BPDC is prepared by a solvothermal method, and the synthetic route is as follows:
TPPP+BPDC+Zn 2+ →Zn-TPPP-BPDC；
the metal zinc salt is selected from one of zinc nitrate, zinc chloride or zinc sulfate;
the main organic ligand TPPP has the following molecular structural formula (A),
the auxiliary ligand BPDC has the following molecular structural formula (B),
the preparation method of the Zn-TPPP-BPDC comprises the following steps:
step 1, adding 15-20 g of phenoxazine, 35-40 g of p-bromoiodobenzene, 20-25 g of sodium tert-butoxide and 400-500 mg of cuprous iodide into a three-necked bottle, vacuumizing, introducing nitrogen, circulating for 1-3 times, adding 150-250 mL of pre-deoxygenated dioxane and 1.2-1.5 mL of 1, 2-cyclohexanediamine, and keeping N 2 Reacting for 10-15 h at 100-110 ℃ in the atmosphere, mechanically stirring, cooling to room temperature after the reaction, and adding a reaction solution in a volume ratio of 1: extracting 2-3 times with 2-3 dichloromethane and water, separating liquid, drying the lower organic phase with anhydrous sodium sulfate, filtering, and collecting filtrateSpin-drying to obtain a crude product, and separating by silica gel column chromatography to obtain white solid powder;
step 2, adding the white solid powder prepared in the step 1 into a round-bottom flask, adding 800-1200 mL of dichloromethane, 4-5 g N-bromosuccinimide and 10-15 g of 200-300-mesh silica gel, carrying out reaction in a dark place, reacting at room temperature for 15-20 h, after the reaction is finished, adding 100-200 g of kieselguhr above filter paper at the bottom of a Buchner funnel, carrying out suction filtration to remove the silica gel in the reaction liquid, carrying out rotary evaporation on the filtrate to obtain a crude product, and then separating by using a silica gel column chromatography to obtain white solid powder;
and 3, mixing the white solid powder prepared in the step 2, pyridine boric acid, tetrakis (triphenylphosphine) palladium and anhydrous potassium carbonate according to the weight ratio of 1: 3-4: 0.05-0.15: adding 4-6 mol ratio of the mixture into a three-necked bottle, vacuumizing and introducing nitrogen for 1-3 times, then sequentially adding 100-150 mL of toluene with pre-deoxygenation, 80-90 mL of ethanol with pre-deoxygenation and 40-50 mL of water with pre-deoxygenation, reacting for 40-50 h at 70-80 ℃, cooling the reaction liquid to room temperature, transferring the reaction liquid into a separating funnel, and performing vacuum distillation by using a volume ratio of 1: extracting 3-5 times with dichloromethane and water, separating liquid, drying a lower organic phase with anhydrous sodium sulfate, filtering, spin-drying filtrate to obtain a crude product, and separating by silica gel column chromatography to obtain yellow solid powder, namely the main organic ligand TPPP;
and 4, mixing the main organic ligand TPPP prepared in the step 3, the auxiliary ligand BPDC and the metal zinc salt according to the ratio of 1: 2-2.5: adding 3-4 mol ratio of the mixture into a mixture with the volume ratio of 1: 1-2, adding the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining after ultrasonic assisted dissolution, sealing, placing the hydrothermal reaction kettle in an oven at 85-90 ℃ for reaction for 40-50 h, cooling to room temperature, removing a supernatant, adding ethanol for washing, and centrifuging to obtain orange blocky crystals, namely the target material phenoxazine-based metal organic framework Zn-TPPP-BPDC.
2. Use of a phenoxazinyl metal organic framework prepared according to the method of claim 1 in a photocatalytic reduction reaction of C-F bonds.
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